US4115310A - Liquid crystalline composition - Google Patents

Liquid crystalline composition Download PDF

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Publication number
US4115310A
US4115310A US05/731,645 US73164576A US4115310A US 4115310 A US4115310 A US 4115310A US 73164576 A US73164576 A US 73164576A US 4115310 A US4115310 A US 4115310A
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Prior art keywords
liquid crystalline
nematic liquid
sup
crystalline composition
sub
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US05/731,645
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English (en)
Inventor
Hisato Sato
Masayuki Tazume
Takasi Yamaki
Yutaka Fujita
Yoshi Arai
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Kawamura Institute of Chemical Research
DIC Corp
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Kawamura Institute of Chemical Research
Dainippon Ink and Chemicals Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
    • C07D487/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/54—Additives having no specific mesophase characterised by their chemical composition
    • C09K19/56—Aligning agents

Definitions

  • This invention relates to a liquid crystalline composition suitable for use as a liquid crystal display element of a dynamic scattering mode (to be referred to as a DSM element).
  • DSM elements utilize a strong light scattering phenomenon which occurs when an electric field having an intensity greater than a certain limit is applied to a nematic liquid crystalline substance.
  • a liquid crystalline composition having negative dielectric anisotropy and resulting from the addition of an ionically conductive substance to a nematic liquid crystalline substance is interposed between electrodes, and an electric field having an intensity greater than a certain limit is applied to it, the liquid crystalline molecules are uniformly oriented at a certain angle to the direction of the electric field, and on the other hand, the ion migration occurring in the direction of the electric field causes the liquid crystalline molecules to rotate in the direction of the electric field.
  • Known orienting agents include, for example, tetraalkylammonium salts derived from simple inorganic acids such as hexadecyl trimethyl ammonium bromide disclosed in U.S. Pat. No. 3,656,834, polyamide resins such as VERSAMID-100 (a trademark for a product of General Mill Co.) disclosed in U.S. Pat. No. 3,803,503, and tetraalkyl ammonium salts of benzoic acid derivatives such as a tetraalkyl ammonium salt of p-butoxybenzoic acid disclosed in German OLS No. 2,209,127.
  • VERSAMID-100 a trademark for a product of General Mill Co.
  • benzoic acid derivatives such as a tetraalkyl ammonium salt of p-butoxybenzoic acid disclosed in German OLS No. 2,209,127.
  • a liquid crystalline composition obtained by adding a 1,8diazo-bicyclo(5,4,0) undecene-7 alkyl ammonium salt of benzoic acid optionally having a substituent at the para-position to a nematic liquid crystalline substance can spontaneously form, in the absence of an electric field, a uniform orientation perpendicular to the wall surface, that is, an orientation whereby the long axes of the molecules are aligned perpendicular to the support plate, and has an electric resistivity suitable for dynamic scattering mode without the need to add an ionically conductive substance.
  • liquid crystalline composition comprising a nematic liquid crystalline substance and as an additive, a 1,8-diazo-bicyclo (5,4,0) undecene-7 alkyl ammonium salt of benzoic acid optionally having a substituent at the para-position.
  • X is an amino group, a nitro group, a chlorine atom, a hydrogen atom, or a straight-chain alkyl group containing 1 to 6 carbon atoms
  • R is a straight-chain alkyl group containing 10 to 20 carbon atoms with the proviso that when X is a hydrogen atom or a straight-chain alkyl group containing 1 to 6 carbon atom, R is a straight-chain alkyl group containing 14 to 20 carbon atoms
  • the amount of such a compound is preferably 0.05 to 0.5% by weight, especially preferably 0.1 to 0.3% by weight, based on the weight of the nematic liquid crystalline substance.
  • nematic liquid crystalline substances having negative dielectric anisotropy.
  • nematic liquid crystalline substances are, for example, benzylidene aniline-type nematic liquid crystalline substances of the general formula ##STR2## wherein R 1 and R 2 both represent C n H 2n+1 --, C n H 2n+1 O--, or C n H 2n+1 COO--, in which n is an integer of 1 to 9,
  • azoxybenzene-type nematic liquid crystalline substances of the general formula ##STR3## wherein R 1 is C n H 2N+1 --, or C n H 2n+1 O--, and R 2 is C n H 2n+1 --, C n H 2n+1 O--, or C n H 2n+1 COO--, in which n is an integer of 1 to 9,
  • phenyl benzoate-type nematic liquid crystalline substances of the general formula ##STR4## wherein R 1 is C n H 2n+1 --, or C n H 2n+1 O--, and R 2 is C n H 2n+1 -- or C n H 2n+1 COO--, in which n is an integer of 1 to 9,
  • the 1,8-diazo-bicyclo(5,4,0) undecene-7 alkyl ammonium salts of benzoic acid or para-substituted benzoic acid may be produced by the following method.
  • a first characteristic of the liquid crystalline composition of this invention is that an extremely uniform orientation perpendicular to the wall surface can be formed.
  • the liquid crystalline composition of this invention When the liquid crystalline composition of this invention is filled in a liquid crystal cell, the liquid crystalline molecules are spontaneously oriented extremely uniformly with their long axes being in a direction at right angles to the support plate.
  • the ability of the liquid crystalline composition to be oriented perpendicularly to the wall surface is great when the content of the additive is at least 0.05% by weight. Irrespective of whether the wall surface of the support plate is made of a conductive layer such as tin oxide or indium oxide, or glass, the liquid crystalline molecules are almostly completely oriented perpendicular to the wall surface. Accordingly, DSM elements obtained by using the liquid crystalline composition of this invention do not cause light scattering resulting from non-uniform molecular orientation, and therefore, are completely transparent in the absence of an electric field. Furthermore, the liquid crystalline composition of this invention can retain its ability with uniform orientation at right angles to the wall surface even after it has been used for long periods of time. For example, even when an AC current of 60 Hz is continuously applied to a DSM element comprising the liquid crystalline composition of this invention for more than 10,000 hours, substantially no disturbance occurs in its molecular orientation, and it can still form a clear image display.
  • a second characteristic of the liquid crystalline composition of this invention is that without any special need to add another ionically conductive substance, it has an electric resistivity suitable for dynamic scattering mode.
  • the content of the additive in the liquid crystalline composition of this invention is 0.05 to 0.5% by weight based on the weight of the nematic liquid crystalline substance, it can form a uniform orientation perpendicular to the wall surface, and at the same time, its specific resistivity can be adjusted to 1 ⁇ 10 7 to 1 ⁇ 10 10 ohms-cm.
  • the liquid crystalline composition of this invention whose specific resistivity is limited to the above range has an especially increased light scattering intensity at an impressing voltage of not more than 30 V. Because of this and the aforesaid ability to be oriented uniformly at right angles to the wall surface, the liquid crystalline composition of this invention can form a vivid display image when applied to DSM elements, and are therefore, especially suitable for practical applications.
  • FIG. 1 shows an optical device for photographing the state of liquid crystalline molecules being oriented perpendicular to the wall surface in a liquid crystal cell
  • FIGS. 2 to 6 are photographs (5X) of the oriented states of liquid crystal cells produced in Example 1, FIG. 2 showing an example of the invention, and FIGS. 3 to 6 showing comparisons;
  • FIG. 7 shows a device for measuring the light transmission characteristics and specific resistivity of a liquid crystal cell
  • FIG. 8 is a graphic representation showing the light transmission characteristics of liquid crystal cells produced in Example 1.
  • a nematic liquid crystalline substance of the following formulation was prepared.
  • Two glass sheets each having on its surface a transparent electrode composed of a thin film of tin oxide were arranged parallel to each other with the transparent electrodes facing inwards, thereby to produce a cell with an interelectrode distance of 20 microns.
  • a liquid crystalline composition prepared by adding 0.1% by weight, based on the nematic liquid crystalline substance (A), of 1,8-diazo-bicyclo(5,4,0) undecene-7 hexadecyl ammonium p-aminobenzoate to the nematic liquid crystalline substance (A) was filled in the resulting cell to form a liquid crystal cell (A-1) of the invention.
  • the nematic liquid crystalline substance (A) containing no additive was filled in the cell to form a liquid cell (A-0).
  • liquid crystalline compositions prepared by adding 0.1% by weight, based on the liquid crystalline substance (A), of VERSAMID-100, hexadecyl trimethyl ammonium bromide, and tetrabutyl ammonium p-n-heptylbenzoate, respectively, to the nematic liquid crystalline substance (A) were filled in the cells to form liquid crystal cells (A-2), (A-3) and (A-4).
  • the orientability, the light transmission characteristics and the specific resistivity of the resulting liquid crystal cells were measured by the following methods.
  • a light source, a lens 1, a polarizer 2, a liquid crystal cell 3, a photodetector 4, and a camera 5 are arranged sequentially.
  • the polarizing surface of the polarizer is placed at right angles to the polarized surface of the photodetector, and the state of the liquid crystalline molecules in the liquid crystal cell being oriented perpendicular to the wall surface is photographed.
  • liquid crystal cell (A-1) of this invention is oriented at right angles to the wall surface more uniformly than any other liquid crystal cell in these comparisons.
  • the light transmission characteristic and specific resistivity were measured by the device shown in FIG. 7.
  • the light rays emitted by putting on a tungsten-filament lamp by means of a DC stabilized source are converted to parallel rays by a lens 1, and then pass through a liquid crystal cell 3.
  • an AC voltage with 60 Hz is applied to the liquid crystal cell to vary the voltage continuously from 0 to 50 V.
  • Changes in the intensity of light scattering caused by this are detected by means of a photoelectric amplifier 9 as changes in light transmittance. They are converted to electrical signals and recorded in an X-Y recorder 10.
  • a light transmission characteristic curve shown in FIG. 8 is obtained.
  • the specific resistivity of the liquid crystal cell is determined from the electric current values separately recorded in the X-Y recorder.
  • the specific resistivity values obtained are shown in Table 1.
  • the reference numeral 6 represents a light transmitting terminal; 7, a current measuring terminal; and 8, a terminal for measuring the voltage applied.
  • the liquid crystal cell (A-1) of this invention has a greater light scattering intensity than the comparative liquid crystal cells (A-0), (A-2), (A-3), and (A-4) at an impressing voltage of not more than 30 V.
  • a nematic liquid crystalline substance of the following formulation was prepared.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Liquid Crystal Substances (AREA)
  • Liquid Crystal (AREA)
US05/731,645 1975-10-15 1976-10-13 Liquid crystalline composition Expired - Lifetime US4115310A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP50-124199 1975-10-15
JP50124199A JPS5247584A (en) 1975-10-15 1975-10-15 Nematic liquid crystal composition

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US4115310A true US4115310A (en) 1978-09-19

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US (1) US4115310A (tr)
JP (1) JPS5247584A (tr)
DE (1) DE2646485C3 (tr)
FR (1) FR2328030A1 (tr)
GB (1) GB1531637A (tr)
IT (1) IT1068855B (tr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0033947A2 (en) * 1980-02-12 1981-08-19 Kabushiki Kaisha Toshiba Liquid crystal display element
EP0199211A2 (de) * 1985-04-17 1986-10-29 BASF Aktiengesellschaft Amphiphile flüssigkristalline Verbindungen
US4886344A (en) * 1984-09-11 1989-12-12 Merck Patent Gesellschaft Mit Beschrankter Haftung Electro-optical display element
US4946989A (en) * 1987-07-27 1990-08-07 Showa Shell Sekiyu Kabushiki Kaisha Optically active compound
US5160451A (en) * 1988-02-26 1992-11-03 Merck Patent Gesellschaft Mit Beschrankter Haftung Mechanical component
US20050129874A1 (en) * 2003-12-15 2005-06-16 Eastman Kodak Company Aligned liquid crystal layer containing azolium salts and process for increasing the tilt

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61161546U (tr) * 1985-03-22 1986-10-06

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3888566A (en) * 1972-08-11 1975-06-10 Hitachi Ltd Electro-optical device including an improved liquid crystal composition
US3922067A (en) * 1974-02-22 1975-11-25 Hitachi Ltd Electro-optical display device including an improved liquid crystal composition
US3956168A (en) * 1972-09-05 1976-05-11 Dainippon Ink And Chemicals, Incorporated Liquid crystal compositions
US3963638A (en) * 1974-01-08 1976-06-15 Eastman Kodak Company Liquid crystal compositions, methods and devices
US3966631A (en) * 1973-08-15 1976-06-29 Hitachi, Ltd. Nematic liquid crystal composition

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3888566A (en) * 1972-08-11 1975-06-10 Hitachi Ltd Electro-optical device including an improved liquid crystal composition
US3956168A (en) * 1972-09-05 1976-05-11 Dainippon Ink And Chemicals, Incorporated Liquid crystal compositions
US3966631A (en) * 1973-08-15 1976-06-29 Hitachi, Ltd. Nematic liquid crystal composition
US3963638A (en) * 1974-01-08 1976-06-15 Eastman Kodak Company Liquid crystal compositions, methods and devices
US3922067A (en) * 1974-02-22 1975-11-25 Hitachi Ltd Electro-optical display device including an improved liquid crystal composition

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0033947A2 (en) * 1980-02-12 1981-08-19 Kabushiki Kaisha Toshiba Liquid crystal display element
EP0033947A3 (en) * 1980-02-12 1981-10-21 Tokyo Shibaura Denki Kabushiki Kaisha Liquid crystal display element
US4886344A (en) * 1984-09-11 1989-12-12 Merck Patent Gesellschaft Mit Beschrankter Haftung Electro-optical display element
EP0199211A2 (de) * 1985-04-17 1986-10-29 BASF Aktiengesellschaft Amphiphile flüssigkristalline Verbindungen
EP0199211A3 (de) * 1985-04-17 1987-09-30 BASF Aktiengesellschaft Amphiphile flüssigkristalline Verbindungen
US4946989A (en) * 1987-07-27 1990-08-07 Showa Shell Sekiyu Kabushiki Kaisha Optically active compound
US5160451A (en) * 1988-02-26 1992-11-03 Merck Patent Gesellschaft Mit Beschrankter Haftung Mechanical component
US20050129874A1 (en) * 2003-12-15 2005-06-16 Eastman Kodak Company Aligned liquid crystal layer containing azolium salts and process for increasing the tilt
US7097888B2 (en) * 2003-12-15 2006-08-29 Eastman Kodak Company Aligned liquid crystal layer containing azolium salts and process for increasing the tilt

Also Published As

Publication number Publication date
DE2646485C3 (de) 1978-11-23
JPS5640190B2 (tr) 1981-09-18
FR2328030B1 (tr) 1978-05-26
DE2646485A1 (de) 1977-04-28
JPS5247584A (en) 1977-04-15
DE2646485B2 (de) 1978-03-16
GB1531637A (en) 1978-11-08
FR2328030A1 (fr) 1977-05-13
IT1068855B (it) 1985-03-21

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